A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390 degrees C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2: 1 liter of ZIF-69 can hold approximately 83 liters of CO2 at 273 kelvin under ambient pressure.

Zeolites are one of humanity's most important synthetic products. These aluminosilicate-based materials represent a large segment of the global economy. Indeed, the value of zeolites used in petroleum refining as catalysts and in detergents as water softeners is estimated at $350 billion per year. A major current goal in zeolite chemistry is to create a structure in which metal ions and functionalizable organic units make up an integral part of the framework. Such a structure, by virtue of the flexibility with which metal ions and organic moieties can be varied, is viewed as a key to further improving zeolite properties and accessing new applications. Recently, it was recognized that the Si-O-Si preferred angle in zeolites (145 degrees ) is coincident with that of the bridging angle in the M-Im-M fragment (where M is Zn or Co and Im is imidazolate), and therefore it should be possible to make new zeolitic imidazolate frameworks (ZIFs) with topologies based on those of tetrahedral zeolites. This idea was successful and proved to be quite fruitful; within the last 5 years over 90 new ZIF structures have been reported. The recent application of high-throughput synthesis and characterization of ZIFs has expanded this structure space significantly: it is now possible to make ZIFs with topologies previously unknown in zeolites, in addition to mimicking known structures. In this Account, we describe the general preparation of crystalline ZIFs, discussing the methods that have been developed to create and analyze the variety of materials afforded. We include a comprehensive list of all known ZIFs, including structure, topology, and pore metrics. We also examine how complexity might be introduced into new structures, highlighting how link-link interactions might be exploited to effect particular cage sizes, create polarity variations between pores, or adjust framework robustness, for example. The chemical and thermal stability of ZIFs permit many applications, such as the capture of CO(2) and its selective separation from industrially relevant gas mixtures. Currently, ZIFs are the best porous materials for the selective capture of CO(2); furthermore, they show exceptionally high capacity for CO(2) among adsorbents operating by physisorption. The stability of ZIFs has also enabled organic transformations to be carried out on the crystals, yielding covalently functionalized isoreticular structures wherein the topology, crystallinity, and porosity of the ZIF structure are maintained throughout the reaction process. These reactions, being carried out on macroscopic crystals that behave as single molecules, have enabled the realization of the chemist's dream of using "crystals as molecules", opening the way for the application of the extensive library of organic reactions to the functionalization of useful extended porous structures.